10.1002/chem.202001584
Chemistry - A European Journal
FULL PAPER
K): δ 185.3 {d, JC-Rh = 3.3, Rh-OC(NH)Me}, 184.8 (d, JC-Rh = 66.1, Rh-CIPr),
146.1 (s, Cq-IPr), 137.2 (s, CqN), 129.3 (s, CHp-Ph-IPr), 123.6 (s, CHm-Ph-IPr),
123.4 (s, =CHN), 60.7 (d, JC-Rh = 14.7, =CHcoe), 30.0, 27.8, and 26.9 (all s,
CH2-coe), 28.7 (s, CHMeIPr), 25.7 and 22.9 (both s, CHMeIPr), 24.7 {d, JC-Rh
= 1.5, Rh-OC(NH)Me}. 1H−15N HSQC (40.5 MHz, toluene-d8, 243 K): δ
189.6 (NIPr), 136.8 (HNCOMe). Data for complex 7b: 1H NMR (400.2 MHz,
toluene-d8, 243 K): δ 7.3-7.0 (6H, HPh-IPr), 6.55 (s, 2H, =CHN), 3.85 (d, JH-
=CHN), 6.48 (d, JH-H = 8.5, 2H, Ho-Ph-N), 3.32 (sept, JH-H = 6.7, 4H, CHMeIPr),
3.18 (m, 2H, =CHcoe), 2.1-0.9 (m, 12H, CH2-coe), 1.72 and 1.09 (both d, JH-
= 6.7, 24H, CHMeIPr), 1.69 (s, 3H, SC(NPh)Me). 13C{1H}-APT NMR
H
(100.4 MHz, C6D6, 298 K): δ 196.8 {d, JC-Rh = 3.3, Rh-SC(NPh)Me}, 185.4
(d, JC-Rh = 62.8, Rh-CIPr), 149.6 (s, Cq-Ph-N), 146.8 (s, Cq-IPr), 138.1 (s, CqN),
129.7 (s, CHp-Ph-IPr), 127.9 (s, CHm-Ph-N), 124.7 (s, CHo-Ph-N), 124.5 (s,
=CHN), 124.2 (s, CHm-Ph-IPr), 124.1 (s, CHp-Ph-N), 64.4 (d, JC-Rh = 14.4,
=CHcoe), 30.4, 29.7, and 26.9 (all s, CH2-coe), 29.9 {s, Rh-SC(NPh)Me},
29.3 (s, CHMeIPr), 26.5 and 23.5 (both s, CHMeIPr).
= 2.9, 1H, NH), 3.17 (sept, JH-H = 7.1, 4H, CHMeIPr), 2. 59 (m, 2H,
Rh
=CHcoe), 2.1-0.9 (m, 12H, CH2-coe), 1.62 and 1.13 (both d, JH-H = 7.1, 24H,
CHMeIPr), 1.58 (s, 3H, OC(NH)Me). 13C{1H}-APT NMR (100.4 MHz,
toluene-d8, 243 K): δ 184.7 (d, JC-Rh = 62.4, Rh-CIPr), 184.3 (d, JC-Rh = 3.0,
Rh-OC(NH)Me), 146.6 (s, Cq-IPr), 137.5 (s, CqN), 123.5 (s, =CHN), 54.7 (d,
JC-Rh = 18.0, =CHcoe), 30.2, 27.8, and 26.9 (all s, CH2-coe), 28.7 (s, CHMeIPr),
26.1 and 22.7 (both s, CHMeIPr), 24.6 {d, JC-Rh = 1.5, Rh-OC(NH)Me}.
1H−15N HSQC (40.5 MHz, toluene-d8, 243 K): δ 191.4 (NIPr), 136.6
(HNCOMe).
Preparation of Rh[κ2-N,N-{N(Ph)C(CH3)NPh}](η2-coe)(IPr) (11). The
yellow complex was prepared as described for
7 starting from
CH3C(NPh)NHPh (40 mg, 0.19 mmol), tBuOK (22 mg, 0.20 mmol) and 1
(120 mg, 0.09 mmol) and isolated as a yellow solid. Yield: 115 mg (75%).
Satisfactory elemental analysis could not be obtained. HRMS (ESI+): m/z
Calcd for RhC41H48N4: (M+-coe-H): 699.2929, Found: 699.2874. IR (cm-1):
1593 ν(NCNsym), 1484 ν(NCNasym). 1H NMR (400.2 MHz, C6D6, 298 K): δ
7.36 (d, 2H, Hm-Ph-IPr), 7.31 (t, JH-H = 8.1, 2H, Hp-Ph-IPr), 7.13 (m, 2H, Hm-Ph-
Preparation of Rh[κ2-N,O-{N(Ph)C(O)CH3}](η2-coe)(IPr) (8). The
complex was prepared as described for 7 starting from CH3C(O)NHPh (25
Na), 7.09 (m, 2H, Hm-Ph-IPr), 7.00 (vt, N = 15.5, 2H, Hm-Ph-Nb), 6.86 (d, JH-H
=
t
mg, 0.19 mmol), BuOK (22 mg, 0.20 mmol) and 1 (120 mg, 0.09 mmol)
8.1, 2H, Ho-Ph-Nb), 6.82 (t, JH-H = 7.4, 2H, Hp-Ph-Nb), 6.81 (t, JH-H = 7.4, 2H,
Hp-Ph-Na), 6.55 (s, 2H, =CHN), 6.53 (d, JH-H = 8.1, 2H, Ho-Ph-Na), 4.29 and
2.02 (both sept, JH-H = 6.7, 4H, CHMeIPr), 2.66 (m, 2H, =CHcoe), 1.83 (s,
N(Ph)C(Me)NPh), 2.1-0.9 (m, 12H, CH2-coe), 1.41, 1.24, 1.01, and 0.97 (all
d, JH-H = 6.7, 24H, CHMeIPr). 13C{1H}-APT NMR (100.4 MHz, C6D6, 298 K):
and isolated as a yellow solid. Yield: 77 mg (69%). Anal. Calcd for
C43H58N3ORh: C, 70.19; H, 7.94; N, 5.71. Found: C, 70.67; H, 8.10; N, 5.29.
HRMS (ESI+): m/z Calcd for RhC35H43N3O (M+-coe-H): 624.2456, Found:
624.2462. IR (cm-1): 1543 ν(OCNsym), 1464 ν(OCNasym). 1H NMR (400.2
MHz, C6D6, 298 K): δ 7.33 (m, 2H, Hp-Ph-IPr), 7.27 (m, 4H, Hm-Ph-IPr), 6.94
δ
193.0 (d, JC-Rh = 57.9, Rh-CIPr), 172.3 {d, JC-Rh = 4.0, Rh-
(vt, 2H, N = 15.5, Hm-Ph-N), 6.76 (t, JH-H = 7.7, 1H, Hp-Ph-N), 6.65 (d, JH-H
=
N(Ph)C(Me)NPh}, 150.1 and 148.7 (both s, CqNPh), 148.2 and 146.6 (both
s, Cq-IPr), 137.8 (s, CqNIPr), 129.7 (s, CHp-Ph-IPr), 128.3 and 128.2 (both s,
CHm-Ph-N), 127.3 (s, CHo-Ph-Nb), 124.8 and 123.7 (both s, CHm-Ph-IPr), 124.6
(s, =CHN), 123.4 (s, CHp-Ph-Nb), 122.8 (s, CHo-Ph-Na), 118.9 (s, CHp-Ph-Na),
57.5 (d, JC-Rh = 15.6, =CHcoe), 30.5 (d, JC-Rh = 1.8, CH2-coe), 29.6 and 27.0
(both s, CH2-coe), 29.2 and 28.6 (s, CHMeIPr), 26.9, 27.1, 23.7, and 22.4 (all
s, CHMeIPr), 17.1 (s, Rh-N(Ph)C(Me)NPh).
7.8, 2H, Ho-Ph-N), 6.52 (s, 2H, =CHN), 3.20 (sept, JH-H = 6.7, 4H, CHMeIPr),
2.67 (m, 2H, =CHcoe), 2.1-0.9 (m, 12H, CH2-coe), 1.60 and 1.08 (both d, JH-
= 6.7, 24H, CHMeIPr), 1.56 (s, 3H, OC(NPh)Me). 13C{1H}-APT NMR
H
(100.4 MHz, C6D6, 298 K): δ 185.7 (d, JC-Rh = 61.7, Rh-CIPr), 180.7 {d, JC-
= 3.2, Rh-OC(NPh)Me}, 148.8 (s, Cq-Ph-N), 146.8 (s, Cq-IPr), 137.2 (s,
Rh
CqN), 129.5 (s, CHp-Ph-IPr), 128.1 (s, CHm-Ph-N), 125.9 (s, CHo-Ph-N), 123.9 (s,
=CHN), 123.7 (s, CHm-Ph-IPr), 122.9 (s, CHp-Ph-N), 56.5 (d, JC-Rh = 16.5,
=CHcoe), 30.1 and 29.7 (both d, JC-Rh = 1.3, CH2-coe), 28.8 (s, CHMeIPr),
26.7 (s, CH2-coe), 26.2 and 22.9 (both s, CHMeIPr), 19.7 {d, JC-Rh = 1.1, Rh-
OC(NPh)Me}.
In
situ
Formation
of
Rh[κ2-N,O-{N(Ph)C(O)CH3}]{η2-
PhC≡C(Ph)C=CH2)(IPr) (13). A solution of 8 (31 mg, 0.042 mmol) in
toluene-d8 at 213 K (0.5 mL, NMR tube) was treated with phenylacetylene
(46 μL, 0.42 mmol). Complex 14 was detected immediately at low
temperature. Conversion reached 90 % after 24 h at 298 K. 1H NMR (400.2
MHz, toluene-d8, 298 K): δ 7.4-6.9 (16H, HPh), 6.51 (s, 2H, =CHN), 5.65
Preparation of Rh[κ2-N,S-{HNC(S)CH3}](η2-coe)(IPr) (9). The complex
was prepared as described for 7 starting from CH3C(S)NH2 (11 mg, 0.19
mmol), tBuOK (22 mg, 0.20 mmol) and 1 (120 mg, 0.09 mmol) and isolated
as a yellow solid. Yield: 63 mg (61%). Anal. Calcd for C37H54N3SRh: C,
65.76; H, 8.05; N, 6.22. Found: C, 66.02; H, 7.98; N, 6.05. HRMS (ESI+):
m/z Calcd for RhC29H40N3S: (M+-coe): 565.1992, Found: 565.1991 IR (cm-
1): 3076 ν(NH), 1556 ν(SCNsym), 1460 ν(SCNasym). 1H NMR (400.2 MHz,
C6D6, 298 K): δ 7.28 (m, 2H, Hp-Ph-IPr), 7.21 (m, 4H, Hm-Ph-IPr), 6.48 (s, 2H,
=CHN), 5.83 (br, 1H, NH), 3.33 (sept, JH-H = 6.7, 4H, CHMeIPr), 3.01 (m,
2H, =CHcoe), 2.1-0.9 (m, 12H, CH2-coe), 1.66 and 1.07 (both d, JH-H = 6.7,
24H, CHMeIPr), 1.53 {d, JH-H = 1.0, 3H, SC(NH)Me}. 13C{1H}-APT NMR
(100.4 MHz, C6D6, 298 K): δ 200.1 (d, JC-Rh = 4.5, Rh-SC(NH)Me), 188.2
(d, JC-Rh = 58.2, Rh-CIPr), 146.3 (s, Cq-IPr), 137.9 (s, CqN), 129.6 (s, CHp-Ph-
IPr), 123.9 (s, =CHN), 123.7 (s, CHm-Ph-IPr), 60.8 (d, JC-Rh = 15.1, =CHcoe),
33.8 {d, JC-Rh = 2.1, Rh-SC(NH)Me}, 30.2 (d, JC-Rh = 1.4, CH2-coe), 29.4 and
26.9 (both s, CH2-coe), 28.9 (s, CHMeIPr), 26.0 and 23.2 (both s, CHMeIPr).
1H−15N HSQC (40.5 MHz, toluene-d8, 243 K): δ 197.9 (HNCSMe), 190.8
(NIPr).
and 5.22 (both d, JH-H = 2.1, 2H, =CH2), 3.03 and 2.92 (both sept, JH-H
=
6.7, 4H, CHMeIPr), 1.41, 1.12, 1.04, and 1.01 (all d, JH-H = 6.7, 24H,
CHMeIPr), 1.76 (s, 3H, OC(NPh)Me). 13C{1H}-APT NMR (100.4 MHz,
toluene-d8, 298 K): δ 184.0 (d, JC-Rh = 58.0, Rh-CIPr), 181.6 (d, JC-Rh = 3.1,
Rh-OC(NPh)Me), 147.2 and 147.1 (both s, Cq-IPr), 141.1 (s. C=CH2), 138.0
(s, CqN), 136.4 (s, Cq-Ph), 130-120 (CHPh), 122.3 (s, =CHN), 123.6 (s, Cq-
Ph), 120.1 (s, =CH2), 86.0 (d, JC-Rh = 18.3, PhC≡CC(Ph)CH2), 82.6 (d, JC-
Rh = 19.3, PhC≡CC(Ph)CH2), 28.8 and 28.6 (both s, CHMeIPr), 26.2, 26.1,
23.2, and 22.7 (all s, CHMeIPr), 19.6 {s, Rh-OC(NPh)Me}.
In
MeOOCC≡CCOOMe)(IPr) (14). A solution of 8 (21 mg, 0.029 mmol) in
toluene-d8 at 243 (0.5 mL, NMR tube) was treated with
situ
Formation
of
Rh[κ2-N,O-{N(Ph)C(O)Me}]{η2-
K
dimethylacetylendicarboxylate (4 μL, 0.32 mmol). NMR measurements
were made immediately. 1H NMR (400.2 MHz, toluene-d8, 243 K): δ 7.19
(m, 2H, Hp-Ph-IPr), 7.08 (m, 4H, Hm-Ph-IPr), 7.01 (vt, 2H, N = 15.7, Hm-Ph-N),
6.75 (t, JH-H = 7.4, 1H, Hp-Ph-N), 6.56 (d, JH-H = 8.3, 2H, Ho-Ph-N), 6.26 (s, 2H,
=CHN), 3.54 and 2.93 (both sept, JH-H = 6.7, 4H, CHMeIPr), 3.18 (s, 6H,
COOMe), 1.82, 1.69, 1.17, and 1.12 (all d, JH-H = 6.7, 24H, CHMeIPr), 1.31
(s, 3H, OC(NPh)Me). 13C{1H}-APT NMR (100.4 MHz, toluene-d8, 243 K):
δ 183.4 (s, Rh-OC(NPh)Me), 176.0 (d, JC-Rh = 56.7, Rh-CIPr), 157.8 (s,
COOMe), 147.3 and 146.5 (both s, Cq-IPr), 145.1 (s, Cq-Ph-N), 135.9 (s, CqN),
130.0 (s, CHp-Ph-IPr), 128.8 (s, CHm-Ph-N), 124.9 (s, =CHN), 124.8 and 124.2
Preparation of Rh[κ2-N,S-{N(Ph)C(S)CH3}](η2-coe)(IPr) (10). The
complex was prepared as described for 7 starting from CH3C(S)NHPh (28
t
mg, 0.19 mmol), BuOK (22 mg, 0.20 mmol) and 1 (120 mg, 0.09 mmol)
and isolated as a yellow solid. Yield: 82 mg (70%). Satisfactory elemental
analysis could not be obtained. HRMS (ESI+): m/z Calcd for RhC35H44N3S:
(M+-coe): 641.2305 Found: 641.2308. IR (cm-1): 1592 ν(SCNsym), 1464
ν(SCNasym). 1H NMR (400.2 MHz, C6D6, 298 K): δ 7.27 (m, 6H, HPh-IPr),
6.84 (vt, 2H, N = 14.7, Hm-Ph-N), 6.72 (t, JH-H = 7.7, 1H, Hp-Ph-N), 6.52 (s, 2H,
(both s, CHm-Ph-IPr), 124.0 (s, CHo-Ph-N), 122.9 (s, CHp-Ph-N), 86.1 (d, JC-Rh
=
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